JPH07107087B2 - Process for producing copolymer of ethylene and vinyl ester - Google Patents
Process for producing copolymer of ethylene and vinyl esterInfo
- Publication number
- JPH07107087B2 JPH07107087B2 JP62109054A JP10905487A JPH07107087B2 JP H07107087 B2 JPH07107087 B2 JP H07107087B2 JP 62109054 A JP62109054 A JP 62109054A JP 10905487 A JP10905487 A JP 10905487A JP H07107087 B2 JPH07107087 B2 JP H07107087B2
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- Prior art keywords
- ethylene
- tributary
- vinyl ester
- temperature
- polymerization
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は、管状反応器中で500バール以上の圧力で共重
合させることによる、エチレンとビニルエステルの共重
合体の製法に関する。さらに詳しくは本発明は、エチレ
ン100重量部をビニルエステル0.1〜30.0重量部と、連続
作業する管状重合系中で、500〜5000バールの圧力及び5
0〜450℃の温度で、ラジカルに分解する重合開始剤の存
在下に、重合系にエチレン、ビニルエステル、開始剤及
び必要に応じ調節剤からの混合物を、重合系の流入部に
おける主流と同時にその流入部の後方での少なくとも２
個の支流により供給して共重合させることによる、エチ
レンとビニルエステルの共重合体の製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for preparing a copolymer of ethylene and vinyl ester by copolymerizing in a tubular reactor at a pressure of 500 bar or higher. More particularly, the invention relates to 100 parts by weight of ethylene and 0.1 to 30.0 parts by weight of vinyl ester in a continuously operating tubular polymerization system at a pressure of 500 to 5000 bar and 5
At a temperature of 0 to 450 ° C., in the presence of a polymerization initiator that decomposes into radicals, a mixture of ethylene, vinyl ester, an initiator and optionally a regulator is added to the polymerization system at the same time as the main flow in the inflow section of the polymerization system. At least 2 behind the inflow
The present invention relates to a method for producing a copolymer of ethylene and vinyl ester by supplying by a single tributary and copolymerizing.
エチレンの高圧重合法において、エチレン流を数個の分
流に分け、主流を開始温度に加熱したのち管状反応器の
入口部に導入することは既知である。この公知方法にお
いて他の１個又は数個の支流は、重合されるエチレンの
流れ方向に沿つて反応器の１個又は数個の位置で供給さ
れる。冷エチレンは、反応器中の重合混合物が許容され
る最高の重合温度を越えた位置又はその少し後の位置で
導入される。その場合導入される冷エチレン（同様に開
始剤を含有する）の温度は、反応器中で混合したのちの
温度が、エチレン重合の開始温度（使用触媒によつて異
なる）より低くならないように定められる（英国特許10
10847号、915210号及び1347361号参照）。In the high-pressure ethylene polymerization process, it is known to divide the ethylene stream into several substreams, heat the main stream to the starting temperature and then introduce it at the inlet of the tubular reactor. In this known process, one or several other tributaries are fed at one or several points in the reactor along the direction of ethylene flow to be polymerized. Cold ethylene is introduced at a position in the reactor above or shortly after the maximum allowable polymerization temperature of the polymerization mixture. The temperature of the cold ethylene (also containing the initiator) introduced in that case should be such that the temperature after mixing in the reactor does not fall below the starting temperature for ethylene polymerization (depending on the catalyst used). (UK patent 10
See 10847, 915210 and 1437361).
このようにして導通量に対するエチレンからポリエチレ
ンへの変化率を高めることができる。この既知方法にお
いては、エチレンに例えば圧縮の前又は後に重合開始剤
としての空気酸素を添加する。空気酸素の代わりに、過
酸化物又はヒドロ過酸化物あるいは過酸化化合物の混合
物を添加することもできる（米国特許3725378号参
照）。In this way, the rate of change from ethylene to polyethylene with respect to the amount of conduction can be increased. In this known method, ethylene is added, for example, with atmospheric oxygen as a polymerization initiator before or after compression. Instead of air oxygen, it is also possible to add a mixture of peroxides or hydroperoxides or peroxide compounds (see US Pat. No. 3,725,378).
これらの既知方法は、生成物が引張り引裂きに対し安定
性が不足するか、あるいは改善された引張り引裂き腐食
に対す安定性を有する生成物を得ようとすると、不経済
な操作をせねばならないという欠点を有する。既知方法
は不経済である。なぜならばビニルエステルを主として
主流に添加する場合は、理論的には引張り引裂き腐食に
対し最高の安定性を有する生成物が得られるはずである
が、コモノマーの調節作用によつて高い溶融指数の生成
物が生じ、これが低分子量合体部の量が高いため引張り
引裂き腐食性に対し明らかに不適当であり、それゆえ開
始剤濃度又は反応温度を低くすることが必要となり、そ
れは変化率を著しく低下させることを意味するからであ
る。It is said that these known methods require uneconomical operation in order to obtain a product having insufficient stability against tensile tearing or to obtain a product having improved stability against tensile tearing corrosion. It has drawbacks. Known methods are uneconomical. The reason is that when vinyl ester is added mainly to the main stream, theoretically the product with the highest stability against tensile tear corrosion should be obtained, but the high melting index formation due to the co-monomer control action. Is produced, which is clearly unsuitable for tensile tearing corrosion due to the high amount of low molecular weight coalesce, and therefore requires a low initiator concentration or reaction temperature, which significantly reduces the rate of change. It means that.
本発明の課題は、エチレンをビニルエステルと管状重合
系中で共重合させる方法において、良好な変化率を保持
したままで、共重合体から製造される生成物の機械的強
度そして特に引張り引裂き腐食に対する安定性を改善す
ることを可能にする方法を提供することであつた。The object of the present invention is, in a process for the copolymerization of ethylene with vinyl esters in tubular polymerization systems, the mechanical strength and especially the tensile tear corrosion of the products produced from the copolymer, while retaining good conversion. It was to provide a method that makes it possible to improve the stability against.
本発明はこの課題を解決するもので、エチレン100重量
部をビニルエステル0.1〜30.0重量部と、連続作業する
管状重合系中で、500〜5000バールの圧力及び50〜450℃
の温度で、ラジカルに分解する重合開始剤の存在下に、
重合系にエチレン、ビニルエステル、開始剤及び必要に
応じ調節剤からの混合物を、重合系の流入部における主
流と同時にその流入部の後方での少なくとも２個の支流
により供給して共重合させ、その際支流（Ｉ）は反応温
度が重合熱により生じた最高温度を越えた位置で、そし
て支流（II）はエチレンの流れ方向に関し支流（Ｉ）の
供給部の前でかつそれぞれの最高温度の位置より前の位
置で供給することを特徴とする、エチレンとビニルエス
テルの共重合体の製法である。The present invention is to solve this problem, 100 parts by weight of ethylene and 0.1 to 30.0 parts by weight of vinyl ester, in a continuous tubular polymerization system, a pressure of 500 to 5000 bar and 50 to 450 ° C.
In the presence of a polymerization initiator that decomposes into radicals at
A mixture of ethylene, a vinyl ester, an initiator and optionally a regulator is fed to the polymerization system at the same time as the main flow in the inflow section of the polymerization system and at least two tributaries behind the inflow section to be copolymerized, In this case, the tributary (I) is at a position where the reaction temperature exceeds the maximum temperature generated by the heat of polymerization, and the tributary (II) is in front of the feed section of the tributary (I) with respect to the direction of ethylene flow and of the respective maximum temperature. It is a method for producing a copolymer of ethylene and vinyl ester, which is characterized in that it is supplied at a position before the position.
エチレン−ビニルエステル共重合体とは、前記の温度及
び圧力、好ましくは1500〜3000バールの圧力及び150〜3
50℃の温度において製造されるエチレンの共重合体を意
味する。エチレン−ビニルエステル共重合体は、重合含
有されるコモノマー量が0.2〜30.0重量％好ましくは0.5
〜20.0重量％であり、ASTM−D1238−65Tにより190℃の
温度及び2.16kgの荷重において測定された溶融指数が0.
1〜25g/10分であり、そしてDIN53479により測定された
密度が0.890〜0.934g/cm3である共重合体である。The ethylene-vinyl ester copolymer is the above-mentioned temperature and pressure, preferably 1500 to 3000 bar and 150 to 3 bar.
It means a copolymer of ethylene produced at a temperature of 50 ° C. Ethylene-vinyl ester copolymer, the amount of comonomer contained by polymerization is 0.2 to 30.0 wt%, preferably 0.5
~ 20.0 wt% and has a melt index of 0,0 measured by ASTM-D1238-65T at a temperature of 190 ° C and a load of 2.16 kg.
Copolymer having a density of 1 to 25 g / 10 minutes and a density of 0.890 to 0.934 g / cm 3 measured according to DIN 53479.
エチレン−酢酸ビニル共重合体及びこれを管状重合系中
で単量体から製造することは、例えば米国特許4048411
号、***特許2617412号及び欧州特許175316号各明細書
に記載されている。Ethylene-vinyl acetate copolymers and their preparation from monomers in tubular polymerization systems are described, for example, in U.S. Pat.
, West German Patent 2617412 and European Patent 175316.
ビニルエステルとしては、前記の温度及び圧力において
エチレンと共重合しうるビニルエステルが用いられる。
そのようなコモノマーは、例えばC1〜C8−好ましくはC1
〜C6−カルボン酸のビニルエステルで特に好ましいもの
は酢酸ビニルである。As the vinyl ester, a vinyl ester which can be copolymerized with ethylene at the above temperature and pressure is used.
Such comonomers are, for example, C 1 -C 8 -preferably C 1
-C 6 -, especially preferred are a carboxylic acid vinyl ester is vinyl acetate.
エチレンとビニルエステルの共重合は、ラジカル開始剤
の存在下に行われる。ラジカル重合開始剤は、高圧下の
エチレンの単独重合にも用いられる触媒である。好適な
ものは、例えば重合されるエチレンに対し好ましくは２
〜100モルppmの量の酸素である。そのほか過酸化物及び
他のラジカル形成体、ならびに種々の分解点を有する過
酸化物及びヒドロ過酸化物の混合物、ならびに酸素及び
過酸化物及び／又はヒドロ過酸化物の混合物も用いられ
る。過酸化物及びヒドロ過酸化物の例としては次のもの
があげられる。三級ブチルパーオキシピバレート、ジ三
級ブチルパーオキシド、三級ブチルヒドロパーオキシ
ド、三級ブチルパーベンゾエート、ｐ−メンタンヒドロ
パーオキシド及びジラウロイルパーオキシド。ラジカル
重合開始剤は、アゾイソ酪酸ジニトリルのような化合物
をも意味する。酸素と１種又は数種の過酸化物との混合
物も使用できる。エチレンとビニルエステルの共重合
を、空気酸素により開始させることが特に好ましい。The copolymerization of ethylene and vinyl ester is carried out in the presence of a radical initiator. The radical polymerization initiator is a catalyst that is also used for homopolymerization of ethylene under high pressure. Suitable are, for example, preferably 2 for ethylene polymerized.
Oxygen in an amount of ~ 100 molar ppm. In addition, peroxides and other radical formers, as well as mixtures of peroxides and hydroperoxides with different decomposition points, and mixtures of oxygen and peroxides and / or hydroperoxides are used. Examples of peroxides and hydroperoxides include the following. Tertiary butyl peroxypivalate, ditertiary butyl peroxide, tertiary butyl hydroperoxide, tertiary butyl perbenzoate, p-menthane hydroperoxide and dilauroyl peroxide. The radical polymerization initiator also means a compound such as azoisobutyric acid dinitrile. Mixtures of oxygen with one or several peroxides can also be used. It is particularly preferred to initiate the copolymerization of ethylene and vinyl ester with atmospheric oxygen.
場合により重合調節剤の存在下で操作する。重合調節剤
によつて、生成するエチレン共重合体の溶融指数を調整
することができる。調節剤としては、例えば水素、ケト
ン、アルデヒド、アルコール、エーテル又は直鎖状もし
くは分岐状の炭化水素が適する。プロパン、プロピレ
ン、メチルエチルケトン又はプロピオンアルデヒドを使
用することが特に好ましい。重合調節剤は一般に、重合
されるエチレンに対し0.2〜５モル％の量で用いられ
る。しかし特別の操作法においては、ビニルエステルが
調節剤としても役立つので、重合調節剤を添加しないで
操作することができる。It is optionally operated in the presence of polymerization regulators. The melting index of the ethylene copolymer produced can be adjusted by the polymerization regulator. Suitable regulators are, for example, hydrogen, ketones, aldehydes, alcohols, ethers or straight-chain or branched hydrocarbons. Particular preference is given to using propane, propylene, methyl ethyl ketone or propionaldehyde. The polymerization regulator is generally used in an amount of 0.2 to 5 mol% based on ethylene to be polymerized. However, in a particular operating mode, the vinyl ester also serves as a regulator, so that it is possible to operate without adding a polymerization regulator.
重合は一般に溶剤の不在で行われる。少量の不活性溶
剤、例えばベンゾール、鉱油又はその他の不活性溶剤
（その中に重合開始剤が溶解される）は、他の使用物質
に対して妨げとならない。重合開始剤として酸素を使用
して操作すると、溶剤は何も使用しないでよい。The polymerization is generally carried out in the absence of solvent. Small amounts of inert solvents, such as benzol, mineral oil or other inert solvents in which the polymerization initiator is dissolved, do not interfere with the other substances used. When operating with oxygen as the polymerization initiator, no solvent may be used.
本方法は、普通の連続的に作業する管状高圧重合系（管
状反応器）を使用して実施することができる。管状反応
器とは、耐圧管の長さ対直径の比が10000〜60000対１の
範囲にある管状の重合容器である。管状反応器を使用す
るエチレンの高圧重合法の詳細は、例えばウルマンス・
エンチクロペデイ・デル・テヒニツシエン・ヘミー1980
年４版、19巻167〜168頁に記載されている。The process can be carried out using conventional continuously operating tubular high pressure polymerization systems (tubular reactors). The tubular reactor is a tubular polymerization vessel in which the length-to-diameter ratio of the pressure tube is in the range of 10,000 to 60,000: 1. Details of the high-pressure polymerization of ethylene using a tubular reactor are described, for example, in Ullmans
Enticlope dei der tehinitsushien hemmy 1980
4th edition, vol. 19, pp. 167-168.
エチレン、ビニルエステル、開始剤及び必要に応じ調節
剤からのガス状混合物は、既知方法により反応器の流入
位置及び同時に反応器の重合されるエチレンの流れ方向
に沿つて流入位置より後方の第二の位置で、反応器に供
給される。流入位置は、一般に管状反応器の入口であ
る。主流は反応器の入口に導入され、支流は既知のよう
に、それ以後で最高温度が生じる位置で供給される。こ
の方法によると既知の２区域管状反応器の反応処理が得
られる。The gaseous mixture from ethylene, vinyl ester, initiator and optionally regulators is added in a known manner to the reactor at the inflow position and at the same time along the flow direction of the polymerized ethylene in the reactor at a second position behind the inflow position. At the position of. The inlet location is generally the inlet of the tubular reactor. The main stream is introduced at the inlet of the reactor and the tributaries are fed, as is known, at the location after which the highest temperature occurs. According to this method, the reaction process of the known two-zone tubular reactor is obtained.
本発明による改良法においては、支流（Ｉ）を反応温度
が重合熱により生ずる最高温度を越した位置に、そして
支流（II）をエチレンの流れ方向に関して支流（Ｉ）の
供給位置より前でそれぞれの最高温度が存在する位置よ
り前の位置に供給する。好ましい操作法によれば、支流
（Ｉ）を反応温度が最高温度を越えた位置に、そして支
流（II）をこの最高温度の前の位置に供給する。この操
作法はいわゆる２区域反応器中で行うことができ、その
場合支流（II）は追加として、進行する反応中の最高温
度の前で供給される。本発明の方法においては、好まし
くは支流（Ｉ）を反応器中の反応混合物が270〜290℃の
温度を有する位置で、そして支流（II）をその前の反応
混合物が最高温度より30〜60℃特に45〜55℃低い温度に
ある位置で供給する。共重合に必要な量のビニルエステ
ルを主として主流及び支流IIにより供給する操作法も特
に好ましい。ガス流の主流対支流Ｉ及び支流IIの割合
は、10:9:1ないし10:5:5の範囲に保たれる。In the improved process according to the invention, the tributary (I) is located at a position where the reaction temperature exceeds the maximum temperature produced by the heat of polymerization, and the tributary (II) is located before the feed position of the tributary (I) with respect to the ethylene flow direction. Supply to a position before the position where the maximum temperature of exists. According to a preferred mode of operation, the tributary (I) is fed to the position where the reaction temperature exceeds the maximum temperature and the tributary (II) is fed to the position before this maximum temperature. This mode of operation can be carried out in a so-called two-zone reactor, in which case the tributary (II) is additionally fed before the maximum temperature during the ongoing reaction. In the process according to the invention, preferably the tributary (I) is at a position in the reactor where the reaction mixture has a temperature of 270-290 ° C. and the tributary (II) is 30-60% above the maximum temperature of the reaction mixture before it. Supply at a temperature lower than 45 ° C, especially 45 to 55 ° C. Particular preference is also given to operating procedures in which the amount of vinyl ester required for the copolymerization is mainly supplied by main stream and tributary II. The main stream to tributary I and tributary II ratios of the gas stream are maintained in the range of 10: 9: 1 to 10: 5: 5.
支流IIを反応器に好ましくは反応混合物の240〜260℃の
温度で導入すると、混合物の温度がまず210〜240℃に低
下し、次いで最高が290〜310℃特に300〜310℃に達す
る。When tributary II is introduced into the reactor, preferably at a temperature of 240 to 260 ° C. of the reaction mixture, the temperature of the mixture first drops to 210 to 240 ° C. and then reaches a maximum of 290 to 310 ° C., in particular 300 to 310 ° C.
本発明の方法によれば、エチレン−ビニルエステル共重
合体から製造された生成物の機械的強度特に引張り引裂
き腐食に対する安全性が改善される。The process according to the invention improves the mechanical strength of products made from ethylene-vinyl ester copolymers, in particular their safety against tensile tear corrosion.
実施例においては、エチレンを２個のガス流に分けて、
前記量の酸素及びコモノマーを添加し、そして2300バー
ルの反応圧まで圧縮する。支流IIは圧搾されたガス流を
一緒にする前に分岐され、そして進行する反応の最高温
度より前の位置で導入され、他の支流（Ｉ）は最高温度
より少し後の位置で導入される。主流は反応器の入口で
供給される。既知の構造を有する管状反応器が用いられ
る。２区域反応器の場合は、支流（II）の導入位置は最
初の反応区域の最高温度の位置より前であり、両方の反
応区域に、対応する最高温度の前にそれぞれ１個の導入
位置を設けることもできる。In the example, ethylene was split into two gas streams,
The above amounts of oxygen and comonomer are added and compressed to a reaction pressure of 2300 bar. Tributary II is branched before combining the compressed gas streams and is introduced at a position prior to the maximum temperature of the proceeding reaction, the other tributary (I) is introduced at a position just below the maximum temperature. . The main stream is fed at the inlet of the reactor. A tubular reactor of known construction is used. In the case of a two-zone reactor, the introduction position of the tributary (II) is before the position of the highest temperature of the first reaction zone, and both reaction zones have one introduction position before the corresponding highest temperature. It can also be provided.
反応器は長さ対直径の比が約10500:1である。重合熱を
誘導除去するため、管壁を外部から水で冷却する。比較
例ではガス流及び支流Ｉだけに、対応する量のビニルエ
ステルを添加し、支流IIを使わないで操作する。得られ
た共重合体は、反応器に後続する分離器中で、既知の方
法により未反応の単量体と分離する。The reactor has a length to diameter ratio of about 10500: 1. In order to remove the heat of polymerization by induction, the tube wall is externally cooled with water. In the comparative example, only the gas stream and the tributary I are added with the corresponding amounts of vinyl ester and the tributary II is not used. The copolymer obtained is separated from unreacted monomers by known methods in a separator following the reactor.
実施例及び比較例 エチレンと酢酸ビニルの共重合を、いずれの場合も管状
反応器中で行つた。エチレンは別個のガス流に分けて、
それぞれ前記量の酸素及びコモノマーを添加したのち、
反応圧力に圧縮した。2300バールの反応圧（反応器の入
口で測定）で、第一導入位置の前で反応混合物は発生す
る反応熱により255℃の温度に達し、支流IIの添加後は
温度は215〜230℃に低下し、そして反応器の中部で第二
導入位置では302℃の最高温度に達した。ガス流には下
記量の酢酸ビニル（VAc）及び酸素を添加した。Examples and Comparative Examples Copolymerization of ethylene and vinyl acetate was carried out in tubular reactors in each case. Ethylene is split into separate gas streams,
After adding the amounts of oxygen and comonomer, respectively,
Compressed to reaction pressure. At a reaction pressure of 2300 bar (measured at the inlet of the reactor), the reaction mixture reaches a temperature of 255 ° C due to the heat of reaction generated before the first introduction position, the temperature reaches 215-230 ° C after the addition of tributary II. It dropped and reached a maximum temperature of 302 ° C. at the second inlet in the middle of the reactor. The following amounts of vinyl acetate (VAc) and oxygen were added to the gas stream.
得られた共重合体の性質及び各例の反応条件ににおける
変化率を、まとめて次表に示す。 The properties of the obtained copolymers and the rate of change in the reaction conditions of each example are summarized in the following table.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 フリードリツヒ・カンネ ドイツ連邦共和国5047ヴエツセリング・ア ントニウスシユトラーセ３ (72)発明者 ジークフリート・クルザーヴエ ドイツ連邦共和国5047ヴエツセリング・フ アザネンウエーク４ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Friedrich Kanne, Federal Republic of Germany 5047 Vwetzelling Antonius Schyutrase 3 (72) Inventor Siegfried Kurservewe, Federal Republic of Germany 5047 Vwetzelling Huazanenwake 4
Claims (4)
30.0重量部と、連続作業する管状重合系中で、500〜500
0バールの圧力及び50〜450℃の温度で、ラジカルに分解
する重合開始剤の存在下に、重合系にエチレン、ビニル
エステル、開始剤及び必要に応じ調節剤からの混合物
を、重合系の流入部における主流と同時にその流入部の
後方での少なくとも２個の支流により供給して共重合さ
せ、その際支流（Ｉ）は反応温度が重合熱により生じた
最高温度を越えた位置で、そして支流（II）はエチレン
の流れ方向に関し支流（Ｉ）の供給部の前でかつそれぞ
れの最高温度の位置より前の位置で供給することを特徴
とする、エチレンとビニルエステルの共重合体の製法。1. 100 parts by weight of ethylene are added to vinyl ester 0.1-.
30.0 parts by weight, 500 to 500 in a tubular polymerization system that operates continuously.
At a pressure of 0 bar and a temperature of 50-450 ° C, in the presence of a polymerization initiator that decomposes into radicals, a mixture of ethylene, a vinyl ester, an initiator and, if necessary, a regulator is introduced into the polymerization system. At the same time as the main flow in the section, by at least two tributaries behind the inflow section, to carry out copolymerization, the tributary (I) being at a position where the reaction temperature exceeds the maximum temperature generated by the heat of polymerization, and (II) is a method for producing a copolymer of ethylene and a vinyl ester, characterized in that the ethylene is fed at a position before the feed part of the tributary (I) with respect to the flow direction of ethylene and before the position of the maximum temperature of each.
た位置で、そして支流（II）をこの最高温度の位置の前
方で供給することを特徴とする、特許請求の範囲第１項
に記載の方法。2. A tributary (I) is fed at a position where the reaction temperature exceeds the maximum temperature and a tributary (II) is fed in front of this maximum temperature. The method described in the section.
度を有する位置で、そして支流（II）をその前方で反応
混合物中の温度が30〜60℃低い位置で供給することを特
徴とする、特許請求の範囲第１項に記載の方法。3. Feeding the tributary (I) at a position where the reaction mixture has a temperature of 270 to 290 ° C. and the tributary (II) at a position in front of which the temperature in the reaction mixture is 30 to 60 ° C. lower. A method as claimed in claim 1, characterized.
して主流及び支流IIにより供給することを特徴とする、
特許請求の範囲第１項に記載の方法。4. The amount of vinyl ester required for copolymerization is supplied mainly by main stream and tributary II.
The method according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3615563.2 | 1986-05-09 | ||
| DE19863615563 DE3615563A1 (en) | 1986-05-09 | 1986-05-09 | METHOD FOR PRODUCING COPOLYMERISATES OF ETHYLENE WITH VINYL ESTERS IN A TUBE REACTOR AT PRESSURES ABOVE 500 BAR |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62263208A JPS62263208A (en) | 1987-11-16 |
| JPH07107087B2 true JPH07107087B2 (en) | 1995-11-15 |
Family
ID=6300407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62109054A Expired - Lifetime JPH07107087B2 (en) | 1986-05-09 | 1987-05-06 | Process for producing copolymer of ethylene and vinyl ester |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4794004A (en) |
| EP (1) | EP0244855B1 (en) |
| JP (1) | JPH07107087B2 (en) |
| AT (1) | ATE94175T1 (en) |
| DE (2) | DE3615563A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4010271A1 (en) * | 1990-03-30 | 1991-10-02 | Basf Ag | METHOD FOR PRODUCING ETHYLENE POLYMERISATS AT PRESSURES ABOVE 500 BAR IN A PIPE REACTOR WITH INJECTION FINGER |
| DE4027140A1 (en) * | 1990-08-28 | 1992-03-05 | Basf Ag | ETHYLENE / VINYL ACETATE COPOLYMERISATES WITH INCREASED RESISTANCE POINT |
| DE4431613A1 (en) * | 1994-09-05 | 1996-03-07 | Peroxid Chemie Gmbh | Process for the production of ethylene copolymers |
| WO2004026923A2 (en) * | 2002-09-20 | 2004-04-01 | Exxonmobil Chemical Patents Inc. | Supercritical polymerization process and polymers produced therefrom |
| US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
| JP5268087B2 (en) * | 2004-07-08 | 2013-08-21 | エクソンモービル・ケミカル・パテンツ・インク | Polymer production under supercritical conditions |
| US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
| US8143352B2 (en) * | 2006-12-20 | 2012-03-27 | Exxonmobil Research And Engineering Company | Process for fluid phase in-line blending of polymers |
| US8080610B2 (en) | 2007-03-06 | 2011-12-20 | Exxonmobil Research And Engineering Company | Monomer recycle process for fluid phase in-line blending of polymers |
| WO2008150572A1 (en) | 2007-06-04 | 2008-12-11 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
| EP2201042B1 (en) * | 2007-09-13 | 2012-06-27 | ExxonMobil Research and Engineering Company | In-line blending of plasticizers with a base polymer |
| US7928162B2 (en) * | 2007-09-13 | 2011-04-19 | Exxonmobil Research And Engineering Company | In-line process for producing plasticized polymers and plasticized polymer blends |
| WO2009082463A1 (en) * | 2007-12-20 | 2009-07-02 | Exxonmobil Research And Engineering Company | In-line process to produce pellet-stable polyolefins |
| US8138269B2 (en) * | 2007-12-20 | 2012-03-20 | Exxonmobil Research And Engineering Company | Polypropylene ethylene-propylene copolymer blends and in-line process to produce them |
| US7910679B2 (en) * | 2007-12-20 | 2011-03-22 | Exxonmobil Research And Engineering Company | Bulk homogeneous polymerization process for ethylene propylene copolymers |
| US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
| CN102282180B (en) * | 2009-01-16 | 2013-11-20 | 巴塞尔聚烯烃股份有限公司 | Method for ethylene polymerization in a tubular reactor with reduced output |
| CN102281943B (en) | 2009-01-16 | 2016-01-20 | 巴塞尔聚烯烃股份有限公司 | Ethylene polymerization in the high-pressure reactor improving initiator feed |
| KR20170084129A (en) | 2014-11-10 | 2017-07-19 | 바스프 에스이 | Ethylene-propylheptyl(meth-)acrylate copolymers |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725378A (en) * | 1958-12-17 | 1973-04-03 | Monsanto Co | Polymerization of ethylene |
| DE1520227A1 (en) * | 1960-03-07 | 1970-01-02 | Monsanto Co | Process for the copolymerization of ethylene and vinyl acetate |
| NL282622A (en) * | 1961-09-01 | |||
| DE1645639B2 (en) * | 1966-09-02 | 1974-12-19 | Veb Leuna-Werke Walter Ulbricht, X 4220 Leuna | Process for the production of ethylene homo- or copolymers |
| US3917577A (en) * | 1968-09-20 | 1975-11-04 | Basf Ag | Continuous production of ethylene homopolymers |
| DE1795365A1 (en) * | 1968-09-20 | 1972-01-05 | Basf Ag | Process for the continuous production of ethylene homopolymers |
| CH536325A (en) * | 1970-08-07 | 1973-04-30 | Imhico Ag | Verfahren zur Homo- und Copolymerisation von Äthylen und Polymerisationsreaktor zu dessen Durchführung |
| DE2508284C3 (en) * | 1975-02-26 | 1985-01-31 | Ruhrchemie Ag, 4200 Oberhausen | Process for the polymerization of ethylene |
| DE2524230A1 (en) * | 1975-05-31 | 1976-12-16 | Basf Ag | PROCESS FOR THE PRODUCTION OF MIXED POLYMERIZES OF ETHYLENE |
| DE2617412C2 (en) * | 1976-04-21 | 1982-02-11 | Basf Ag, 6700 Ludwigshafen | Process for the production of copolymers of ethylene |
| US4135044A (en) * | 1977-08-08 | 1979-01-16 | Exxon Research & Engineering Co. | Process for achieving high conversions in the production of polyethylene |
| DE3404742A1 (en) * | 1984-02-10 | 1985-08-14 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING COPOLYMERISATES OF ETHYLENE WITH COMONOMERS CONTAINING CARBOXYL GROUPS IN A 2-ZONE REACTOR AT PRESSURES ABOVE 500 BAR |
| DE3434316A1 (en) * | 1984-09-19 | 1986-03-27 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF ETHYLENE COPOLYMERS |
-
1986
- 1986-05-09 DE DE19863615563 patent/DE3615563A1/en not_active Withdrawn
-
1987
- 1987-04-22 US US07/041,231 patent/US4794004A/en not_active Expired - Lifetime
- 1987-05-06 JP JP62109054A patent/JPH07107087B2/en not_active Expired - Lifetime
- 1987-05-07 AT AT87106593T patent/ATE94175T1/en not_active IP Right Cessation
- 1987-05-07 EP EP87106593A patent/EP0244855B1/en not_active Expired - Lifetime
- 1987-05-07 DE DE87106593T patent/DE3787310D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3787310D1 (en) | 1993-10-14 |
| JPS62263208A (en) | 1987-11-16 |
| ATE94175T1 (en) | 1993-09-15 |
| EP0244855A3 (en) | 1990-09-19 |
| DE3615563A1 (en) | 1987-11-12 |
| EP0244855A2 (en) | 1987-11-11 |
| EP0244855B1 (en) | 1993-09-08 |
| US4794004A (en) | 1988-12-27 |
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